Carbon 1966,Vol. 4, pp. 255-262. Pergamon Press Ltd.

Printed in Great Britain

THE ADSORPTION OF OXYGEN ON BROWN COAL CHAR

D. J. ALLARDICE

Brown Coal Research Laboratory, Department of Chemical Engineering,

University of Melbourne, Parkville, Victoria, Australia

(Received 22 November 1965)

Abstract-The adsorption of oxygen on degassed brown coal char has been investigated gravimetrically
in the temperature range 25”-200°C and at pressures up to 1 atm. The adsorption occurs by two
separate processes, one reversible and the other irreversible. Methods have been devised to investigate
these processes independently. The reversible adsorption was found to be physical adsorption, while the
irreversible process is a chemisorption conforming to the Elovich equation. A mechanism for this latter
process has been suggested, involving rate control by a surface migration phenomenon.

1. INTRODUCTION
WHILE investigating the application of brown coal
char as a metallurgical fuel, it was found that pro-
longed exposure of the char to the atmosphere
affected its combustion properties. BREEN and
EVANS(~) attributed this effect to the adsorption of
atmospheric oxygen and water vapour on to the
char. In the light of their work a more detailed in-
vestigation was conducted into the adsorption of
oxygen on brown coal char both to obtain basic
information on the nature of this adsorption
phenomenon and to provide technical data on the
extent and rates of the processes involved.
Preliminary results reported by the author(‘)
established that the adsorption of oxygen on de-
gassed brown coal at temperatures below 200°C
occurs by two separate concurrent processes, one a
rapid reversible equilibrium process and the other
a slow irreversible process. The reversibly ad-
sorbed oxygen was defined as the oxygen adsorbed
on the degassed sample which could be reversibly
desorbed by evacuation at the same temperature.
Conversely, the irreversibly adsorbed oxygen was
defined as oxygen which could not be desorbed by
isothermal evacuation.
In the present work the phenomena of reversible
and irreversible adsorption of oxygen on brown
coal char have been investigated in more detail,
particularly with regard to temperature and
pressure dependence, in order to characterize the
processes involved.
2. EXPERIMENTAL
The apparatus used was the modified McBain-
Bakr sorption balance described previously. The
samples used in this work were from a Yallourn
brown coal I-type briquette carbonized at 1000°C
and ground in air to pass a 72 mesh B.S. sieve. The
adsorption processes were studied at oxygen
pressures up to one atmosphere and temperatures
from 25” to 200°C. The lower temperature limit
was arbitrarily fixed by ambient conditions, while
the upper temperature was limited by the possi-
bility of simultaneous desorption of oxides of
carbon which occurs with chars at temperatures
above 250”-300”C.~1*3~ In a preliminary experi-
ment, no desorption of these species was detected
during the adsorption of oxygen on brown coal char
at 200°C so that it is valid to trace the adsorption
gravimetrically below this temperature.
2.1 Reversible adsorption
The reversible adsorption was studied by main-
taining the amount of irreversibly adsorbed oxygen
constant. This was achieved by conducting experi-
ments on a sample which had been degassed under
vacuum at 1000°C for 10 hr and then exposed to
oxygen for several days at 25°C and 760 mm/Hg
pressure, by which time the increase in weight of
the sample due to the continuous irreversible
adsorption was negligible over a period of hours.@)
Thus any change in the total amount adsorbed
over a short time was due to the variation in

255
256 D. J. ALLARDICE
400
Reswre , mmHg
FIG. 1. Isotherms for the reversible adsorption of oxygen
on brown coal char.
reversible adsorption with temperature or pressure.
Adsorption isotherms were therefore constructed
by maintaining the temperature constant and
varying the pressure. The isotherms obtained in
this manner for reversibly adsorbed oxygen at
temperatures from 25°C to 200°C are represented
in Fig. 1.
The reversible adsorption process showed no
evidence of hysteresis effects in the temperature
and pressure range investigated, as identical
curves were obtained for adsorption and desorp-
tion isotherms.
Some measurements were also made on samples
of differing pretreatment. For example, one sample
was degassed under vacuum at 1000°C for 10 hr
and then exposed to hydrogen for 1 hr at 25°C and
1 atm prior to exposure to oxygen. Another sample
was degassed in a stream of oxygen-free nitrogen
at 1000°C for 10 hr. In Figure 2 the reversible
adsorption of oxygen on these samples at different
temperatures is compared with the results ob-
tained for a standard sample degassed under
vacuum at 1000°C for 10 hr. This figure shows
that the amount of oxygen reversibly adsorbed
does not depend on the pretreatment of the sample.
I I I I -1
100 200
Temperature,T.
FIG. 2. Effect of sample pretreatment on the reversible
adsorption of oxygen on brown coal char at a pressure of
760 mm Hg.
+ Sample degassed under vacuum;
x Sample degassed in oxygen-free nitrogen;
0 Sample pretreated with hydrogen after degassing
under vacuum.
2.2 Irreversible adsorption
From the detmitions of reversible and irrever-
sible adsorption used in the present work, it
follows that the amount of irreversibly adsorbed
oxygen at any time (qir) is the difference between
the total amount adsorbed (qtot) and the amount
reversibly adsorbed (qr) at that time
i.e. qir = qtot - qr (1)
After the first 5 min of an adsorption run, qr
reaches a constant equilibrium value which can be
determined by isothermal evacuation at the com-
pletion of the run. Thus the irreversible adsorp-
tion at any time after the first 5 mm can be deter-
mined by subtracting the equilibrium value of qr
from the measured value of qtot at that time.
A typical irreversible adsorption is represented
in Fig. 3 where qir has been calculated by the
method outlined above. In all such experiments
the rate of the irreversible adsorption (given by the
slope of the curve) decreases with time. This is a
 THE ADSORPTION OF OXYGEN ON BROWN COAL CHAR 257

or 4 =2.3/a [log (t+t,)-log t,J (4)

<
where a, a and t, are constants (t,= l/au)
If applicable to an adsorption system, the
Elovich equation has three main functions.
Firstly it provides a convenient method of graph-
ing and interpolating the data. Secondly, it per-
mits calculation of instantaneous rates of adsorp-
I
tion by graphical evaluation of a and substitution
300
Ttme , minutes in equation (2). Thirdly, it provides a means of
FIG. 3. Oxygen irreversibly adsorbed (qir) on degassed extrapolating the data to determine the initial rate
brown coal char at 25°C and 760 mm Hg. of irreversible adsorption which cannot be meas-
ured directly because of the simultaneous rever-
common phenomenon in adsorption systems, sible adsorption process. In fact, equation (2)
leading to serious problems in analysing the shows that the Elovich constant a is the initial rate
kinetics of the adsorption process by classical of adsorption when qir =O.
methods. TAYLOR and THON(~) suggested that an arbi-
As the irreversible adsorption proceeds, the trary value oft, be selected to give a linear plot of q
number of sites available for adsorption should against log (t+t,J. In the present study this was
decrease in a linear manner, but this is not suffi- not necessary, as a plot of qir against log t was
cient to account for the observed variation in rate. quite linear after the initial period during which
(In the present work the rate decreased exponen- reversible adsorption occurs. The slope of the line
tially with the amount of oxygen irreversibly ad- obtained gave a value for a which was then substi-
sorbed as will be shown later). In fact, at present tuted in equation (3) with values of qir and t at any
there is no accepted theory to explain this pheno- point on the line to evaluate the initial rate a. It
menon of decreasing rates of adsorption. There- should be stressed that the quantity q substituted
fore it is necessary to resort to empirical methods in the Elovich equation was qir and not qtot as the
of correlating qir with 5, in order to calculate instan- latter quantity included oxygen adsorbed by a
taneous rates of adsorption which can be used in a different process (reversible adsorption).
kinetic analysis. In approaching this problem, the In order to obtain reproducible results, a fresh
author tried several equations, for example, the sample of char was used for each of the adsorption
parabolic diffusion equation, without success. runs conducted, because successive adsorption-
However, it was found that a plot of qir against log degassing cycles on the same sample caused signi-
t was linear for all the adsorption runs conducted ficant deactivation. For example, successive values
in this work. TAYLOR and THON(~) have shown calculated for the initial rate of adsorption a on the
mathematically that this relationship is evidence of same sample under identical conditions were 7.7,
an adsorption process which conforms to the 4.9 and 3.4 mg/g per min. This effect is due to
Elovich equation. irreversible surface changes during the degassing
2.3 Application of the Elovich equation step, possibly caused by the destruction of adsorp-
The Elovich equation is an empirical relation- tion sites or loss of mineral matter* which could
ship which has found wide application in kinetic act as a catalyst for the adsorption.
studies of sorption processes, particularly in the In the present work, the irreversible adsorption
field of chemisorption. The equation can be ex- process was investigated by evaluating the
pressed as Elovich constants a and a for adsorption runs con-
ducted at different temperatures and pressures.
dq --I 2.4 Temperature dependence of irreversible adsorption
dt=ae The irreversible adsorption of oxygen at 760 mm
Hg on a degassed sample of brown coal char was
or in the integrated form
*Char from Yallourn brown coal initially has an ash
q =2.3/a log (au f + 1) (3) content of 3-4 per cent.
258 D. J. ALLARDICE

161 mm/

I I J
1 10 100
lime , minutes.

FIG. 4. Elovich plots for the irreversible adsorption of 01 I I J

oxygen at 760 mm Hg pressure and varying temperatures. 1 10 100
Time, minutes.

traced gravimetrically for 300 min at temperatures
varying from 25” to 200°C. Figure 4, the Elovich
plots of these adsorptions, shows that a good linear
relationship is obtained in each case, justifying the
use of the Elovich equation to express the results.
The values of a and a calculated from the lines are
reported in Table 1. The values obtained for a are
highly dependent on temperature, while the
values of a are apparently independent of tempera-
ture. The significance of these results will be
discussed later.
FIG. 5. Elovich plots for the irreversible adsorption of
oxygen at 65°C and at varyinglpressures.
2.5 The pressure dependence of the irreversible
adsorption
A series of adsorption runs was conducted at
65°C and various oxygen pressures from 160 to 760
mm/Hg. The results obtained were plotted on an
Elovich scale (Fig. 5) and again there was a linear
relationship in each case. Values of a and a calcu-
lated as before are reported in Table 2. The

TABLE 1. THE TEMPERATURE DEPENDENCE OF TIiE ELOVICH TABLE 2. tiE PRE8SURE DEPENDENCE OF THE ELOVICH
CONSTANTS

Temperature Pressure CJ Temperature Pressure

(“C) (mm Hg) (mglg per min) (mgYgY (“Cl (mm Hg) (mglg ;er min) (mgyg)-l

25 760 1.15 1.07 65 161 11.2 1.65

65 760 7.66 1.09 65 282 12.2 146
110 760 101 1.09 65 454 10.7 1.30
155 760 292 1 .Ol 65 608 12.5 1.21
200 760 1160 1 *Ol 65 760 12.3 1.07
 THE ADSORPTION OF OXYGEN ON BROWN COAL CHAR
initial rate a is apparently independent of pressure
but a definite correlation exists between u and the
oxygen pressure though the exact form of this
dependence cannot be clearly established from the
limited data available.
3. DISCUSSION
Recently LANGHOFF and PETERS(‘) using gravi-
metric techniques reported the simultaneous
physical adsorption and chemisorption of oxygen on
hard coals at low temperatures. ERGUN@)has also
suggested that physically and chemically adsorbed
oxygen can occur on carbon. The present writer(*)
has established the existence of two simultaneous
processes for the adsorption of oxygen on brown
coal char, one reversible and the other irreversible.
In the following discussion, the results obtained in
the present work are used to establish that
(1) the reversible effect is actually physical ad-
sorption,
(2) the irreversible effect is a chemisorption
process, conforming to the empirical Elovich
equation, and
(3) the rate controlling step in the irreversible
adsorption is probably a surface migration
phenomenon.
3.1 The nature of reversible adsorption
As the reversible adsorption was an equilibrium
effect which rapidly achieved saturation,(*) the
change in this equilibrium with temperature and
pressure has been investigated in order to charac-
terize the process involved. However, the kinetics
of the reversible adsorption could not be studied
in the apparatus available because the adsorption
was too fast, reaching equilibrium within 5 min.
The critical distinction between physical and
chemical adsorption is the heat of adsorption,
Physical adsorption is characterized by heats of the
same order as the heat of vaporization. HAYWARD
and TRAPNELL quote figures of 16-S kcal/mole
as reasonable limits for the heats of physical
adsorption of oxygen. In contrast, the heats of
chemisorption of gases are generally in the range
20-100 kcal/mole. For instance, BULL, HALL and
GARNER@)have reported a value of 97 kcal/mole
for the heat of chemisorption of oxygen on charcoal.
In the present in~esti~tion of the reversible
adsorption, there were no hysteresis effects
apparent in the isotherms obtained (Fig. 1). Hence
this adsorption can be regarded as thermo-
259
dynamically reversible over the range investigated,
permitting the calculation of isosteric heats of ad-
sorption using the Clausius-Clapeyron relation-
ship for adsorption systems.
The appropriate equations are
or in the integrated form
where p is the oxygen pressure, T the absolute
temperature, Qst the isosteric heat of adsorption,
R the universal gas constant, and Q the amount of
oxygen adsorbed (reversibly) which is directly pro-
portional to the degree of surface coverage. The
subscripts 1 and 2 refer to points on different iso-
therms having the same value of q under different
conditions of temperature and pressure.
The isosteric heats of adsorption calculated from
the data in Fig. 1 using the integrated form of the
Clausius-Clapeyron expression were in the range
46-52 kcal/mole. The values obtained decreased
slightly but systematically with temperature and
coverage. By comparison with the limits quoted
above, these results establish that the reversible
process is physical adsorption. This conclusion is
supported by the experimental observation that
the extent of the reversible process does not
depend on the sample pretreatment.
There are three types of physical adsorption
which could operate in the case of brown coal
char : monolayer adsorption, multi-layer adsorp-
tion and capillary condensation in the pores. Since
multi-layer adsorption and capillary condensation
are improbable because the experiments were con-
ducted well above the critical temperature of
oxygen, it appears that the reversible process is
actually monolayer physical adsorption. This
deduction is consistent with the shape of the iso-
therms in Fig. 1.
The ultimate proof of monolayer adsorption is to
calculate the degree of surface coverage. This
requires an estimate of the surface area; however,
the interpretation of surface area determinations
on carbonaceous materials is still open to ques-
tioncgf and only approximate figures are available
for brown coal chars. (1o-12) By using a conserva-
tive figure of 160 m*/g it was found that less than
260 D. J. ALLARDICE

25.per cent of the surface is covered with reversibly Arrhenius plot (Fig. 6) a meaningless curve with a
adsorbed oxygen at 25°C and 760 mm Hg pressure. distinct minimum (Fig. 7) is obtained, due to the
3.2, The nature of the irreversible adsorption variation in q,. with temperature.
Oxygen irreversibly adsorbed on brown coal
char can only be recovered in a different chemical Temperature, OC.
250 150 50
form, as oxides of carbon.(2) The desorption of c’4.0 f t t
.-
these oxides begins at temperatures of 250”- E
.
300°C but the oxygen cannot be recovered quanti- ?
tatively below 1000°C. (l) Thus by implication, the E”
oxygen must undergo a chemical change during the 0;
adsorption ‘process, i.e. the irreversible adsorption ‘ii
L

is a chemisorption process. This is analogous to the

&assical argument of RHEAD and WHEELER.
3.3 The kinetics of the irrewrsible adsorption
The data obtained in the investigation of the
irreversible adsorption can be expressed by the
empirical Elovich equation

dt
where a and a are constants which can be evaluated L. I I ,

graphically. It should be stressed that for con- 1.5 2.5 3.5

venience the adsorptions were only investigated for l/T(V”I) x IO3
300 min. It is known@) that the adsorption con- FIG. 6. An Arrhenius plot of the initial rates of irrever-
sible adsorption of oxygen on brown coal char at 760 mm
tinues with a decreasing rate for at least several
Hg pressure.
months, but it may not conform to the Elovich
equation for the whole of this period. In fact, a Temperoture. OC.
deviation from Elovich as the sample approaches
saturation can be predicted from assumptions
made in theoretical derivationsti4) of the empirical
equation used. However, in the present investiga-
tion saturated conditions are not reached, and the
data conforms to the Elovich equation throughout
the experimental period.
As mentioned earlier, the Elovich constant a is
actually the initial rate of the irreversible adsorp-
tion when pir =O. As the value of a was indepen-
dent of pressure (Table Z), the initial adsorption is
a zero order reaction. In contrast, a shows a
marked dependence on temperature (Table 1).
When the values of a at different temperatures
were plotted on an Arrhenius scale (Fig. 6), an
activation energy of 1 l-1 + 1.5 kcaljmole was calcu-
lated from the slope. This is the apparent activa-
tion energy for the initial irreversible adsorption of
oxygen on degassed brown coal char. VTPH”‘) x103
FIG. 7. Arrhenius plots comparing the initial rates of
It is worth emphasizing that the initial rates
adsorption calculated from the Elovich equation using
were calculated using qk and not qtot in the (A) the total amount of oxygen adsorbed 13 and (B) the
Elovich equation. If qtot is used, instead of a linear amount irreversibly adsorbed 0.
 THE ADSORPTION OF OXYGEN
The value obtained for activation energy of the
initial irreversible adsorption (11-l + 1.5 kcal/mole)
is rather low for a chemical reaction. However,
other workers(‘5-‘7) have also obtained values of
less than 20 kcal/mole for chemisorption reactions
on carbonaceous materials, Activation energies of
this order are generally attributed to rate control
by some mass transport or diffusion phenomenon.
Rate control by diffusion of oxygen through a
surface film of inert gas or through the pores to
adsorption sites is unlikely at the temperatures
investigated. These eiTccts do not influence the
kinetics of combustion of carbon in oxygen at tem-
peratures below 6.50”C,“8-20’ and the low tempera-
ture chemisorption of oxygen is a much slower
process, and therefore even less likely to be affected.
The most probable explanation of the low
activation energy is that the rate of chemisorption
is controlled by the migration of a mobile physi-
cally adsorbed layer across the surface to active
sites where chemical interaction occurs. This
deduction is supported by the observation that the
initial rate of the irreversible process is indepen-
dent of the oxygen pressure-the reaction being
zero order. According to WALKER, RUSINKO and
AusT&~‘) a zero order gas-solid reaction in which
no desorption is occurring indicates rate control by
the surface rearrangement of adsorbed species. In
the present system, there are two possible surface
rearrangement steps-firstly the surface migration
suggested above, and secondly the conversion of
physically adsorbed oxygen to a chemisorbed
state. The former step is more likely to be con-
trolling the rate because of the low activation
energy of the irreversible adsorption.
For rate control by surface migration, the activa-
tion energy should depend only on the energy
barrier between adjacent adsorption sites, irrespec-
tive of the amount of oxygen chemisorbed on the
surface. This has been investigated in the present
work by comparing instantaneous rates of chemi-
sorption at different coverages over the tempera-
ture range used. These rates were calculated by
substituting the values of a and (y.from Table 1 in
the Elovich equation (2) using different values of 9.
The rates obtained are plotted on an Arrhenius
scale in Fig. 8, which shows that the activation
energy is independent of the amount of oxygen
chemisorbed.
ON BROWN COAL CHAR 261
ipmoerature .‘c+
Z.0 , I
1.5 2.5 3.5
l/T PK-‘1 x lo3
FIG. 8. Arrhenius plots for the rates of irreversible
adsorption calculated from the Elovich equation at
coverages of 0, 4 and 8 mg/g.
It can be shown mathematically that the
constant activation energy is a direct result of the
experimental observation that the Elovich constant
a does not vary with temperature. Normally, chemi-
sorptions conforming to the Elovich equation have
activation energies which increase with coverage(4)
(because c1 decreases with temperature) though
some examples of constant activation energy have
been reported.(22’
If surface migration of physically adsorbed
oxygen is the rate controlling step in the irrever-
sible adsorption, it can be assumed that the rate of
adsorption shows a linear dependence on the con-
centration of physically adsorbed oxygen qr which
varies with temperature (Fig. 2). Rate constants
independent of this effect can be calcuIated at any
temperature by dividing the initial rate n by qr at
that temperature. These modified rate constants
give a corrected activation energy of lSj2 kcal/
mole, which is independent of the concentration
of physically adsorbed oxygen.
4. CONCLUSIONS
In the previous work by the author(‘) it was con-
cluded that the adsorption of oxygen on degassed
brown coal char at low temperatures could be
divided into two concurrent processes, one rever-
sible and the other irreversible. In the present
work, these two processes were investigated in
more detail and the following conclusions were
drawn.
262 D. J. ALLARDICE
(1) The reversible adsorption process was due to
monolayer physical adsorption on the char surface,
the extent depending only on the temperature and
pressure of the system. The isosteric heat of the
reversible adsorption varied from 4.6 to 5.2 kcal/
mole under the conditions investigated.
(2) The irreversible adsorption process con-
formed to the empirical Elovich equation and
arose from the chemisorption of oxygen on the
degassed char surface. This chemisorption was
initially zero order with an apparent activation
energy of 11.1+ la.5 kcal/mole. This activation
energy did not change with coverage.
(3) A suggested mechanism for the adsorption on
degassed brown coal char is that an initial rapid
physical adsorption occurs, followed by the migra-
tion of the physically adsorbed oxygen across the
surface to active sites where chemisorption occurs.
This chemisorption is a slow process for which the
rate decreases exponentially with the coverage of
the surface with chemisorbed oxygen for at least
300 min. The rate controlling step of this chemi-
sorption appears to be the surface migration of the
physically adsorbed species, in which case the
kinetics can be modified by assuming a linear
dependence of the rate on qs, giving a corrected
activation energy of 15 + 2 kcalfmoie.
Acknowledgements-The author thanks the University of
Melbourne for granting a Research Scholarship and
Messrs. D. G. EVANSand G. M. WILLIS for their advice
and constructive criticism throughout the project.
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